CN104004479B - Phenolate lignin tackiness agent and preparing method of phenolate lignin tackiness agent - Google Patents
Phenolate lignin tackiness agent and preparing method of phenolate lignin tackiness agent Download PDFInfo
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- CN104004479B CN104004479B CN201410264173.4A CN201410264173A CN104004479B CN 104004479 B CN104004479 B CN 104004479B CN 201410264173 A CN201410264173 A CN 201410264173A CN 104004479 B CN104004479 B CN 104004479B
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Abstract
The invention discloses a phenolate lignin tackiness agent and a preparing method of the phenolate lignin tackiness agent. Under the normal pressure, phenol serves as a phenolate reagent, lignin and master and slave acid catalysts are added at a certain temperature at four to five times in sequence, the temperature is rose to 100 DEG C-130 DEG C, heat preservation reaction is carried out, cooling is carried out, basic catalysts are added, after the heat preservation reaction is carried out for a certain time, aldehydes materials are added at four times, heat preservation reaction is carried out at 80 DEG C-95 DEG C until the viscosity meets the requirement, water is added to adjust the solid content, and meanwhile rapid cooling is carried to enable the temperature to be lower than 50 DEG C, discharging is carried out, and then the phenolate lignin tackiness agent is obtained. Compared with a traditional phenolate lignin tackiness agent, the prepared phenolate lignin tackiness agent has the advantages that the replacement amount of the lignin to the phenol is as high as 50%-80%, and the cost can be reduced by about 40%. The phenolate lignin tackiness agent prepared with the method is safe, environmentally friendly, good in mobility and good in storage stability. Bamboo/wood plywood manufactured with the phenolate lignin tackiness agent has the good mechanics performance and the good hydrolytic resistance.
Description
Technical field
The invention belongs to natural polymer field, be specifically related to a kind of phenolate xylogen tackiness agent and preparation method thereof.
Background technology
Xylogen is one of the three large main ingredients of plant (Mierocrystalline cellulose, xylogen and hemicellulose), at occurring in nature, be the natural high molecular substance being only second to cellulosic content more than second, and xylogen is the non-oil resource that nature unique energy near-infinite number provides renewable compound aromatic base.Xylogen is mainly derived from the waste liquid of commercial paper slurrying, has inexpensive, renewable, advantages of environment protection.It is generally acknowledged, the complex compound that xylogen is made up of aromatic nucleus class formation unit, multiple functional group is there is in its structure, as functional groups such as hydroxyl, methoxyl group, carbonyl, carboxyl, methyl, their existence in log lignin structure is relevant with the kind of xylogen with distribution, the existence in separating lignin structure with distribute also relevant with extraction and separation method.Just because of there being multi-functional existence perhaps, so xylogen has number of chemical character, number of chemical reaction can be there is.After different treatment is carried out to xylogen, xylogen can be made under certain condition to react with the plurality of raw materials such as aldehyde, isocyanic ester, the materials such as synthesis lignin-base resol, urethane, the pollution to environment such as the consumption of the petroleum resources such as phenol, minimizing paper waste can be saved simultaneously, for resol, xylogen can also reduce the content of resol Free-formaldehyde to a certain extent.This comprehensive utilization to natural resource, protection of the environment all have important economic implications and social effect.
The applied research of xylogen in synvaren is a lot, but the example be really successfully applied in production is little.No matter reason is it is natural lignin or industrial treatment xylogen, its molecular structure is complicated, molecular weight higher (generally its Mw value thousands of arrive hundreds thousand of not etc.), substituent steric hindrance is larger on aromatic nucleus contained by xylogen, can not effectively react with phenol and formaldehyde, and the xylogen of macromolecule also the normal polymerization of Pyrogentisinic Acid and formaldehyde can have certain inhibition.By chemical modification as carried out demethylation to xylogen, methylolation, alkalization synthesize the phenolic glue obtained and compare with unmodified, quality is improved, the patent CN101104782 of this respect, CN101492522, CN101358120, CN101348698 etc.Still there are some problems in the modified phenol formaldehyde resin adhesive with pulping waste liquor stick modified by these methods, as: poor storage stability, viscosity are large, curing reaction speed is slow, mechanical property significantly reduces, especially resistance to boiling water can reduce serious etc., and the addition of xylogen lower (being less than 50%), because the restriction of these factors, make troubles to the actual production of modified phenol formaldehyde resin adhesive with pulping waste liquor stick and application, have impact on the application of modified phenol formaldehyde resin adhesive with pulping waste liquor stick.
The present invention has the feature of high reaction activity after carrying out thermochemistry phenolate according to xylogen, to authorize and on the basis of the industrial applications patented technology of 6 years (CN101260283) the present inventor, through theoretical and experimental study for many years, under the prerequisite ensureing tackiness agent various aspects of performance, significantly improve the usage quantity of xylogen, the alternative amount of xylogen Pyrogentisinic Acid, by the present inventor's granted patent technology (CN101260283) 14.3 ~ 45.5%, is increased to of the present invention 50 ~ 80%.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of environmental friendliness, excellent performance, phenolate xylogen tackiness agent with low cost, the method is simple to operation, be convenient to industrialization, and prepared tackiness agent also has the features such as good fluidity, shelf-stable, easy construction concurrently.Use the impregnated paper of this production of adhesive, bamboo/wood plywood etc., there is the features such as safety and environmental protection, excellent in mechanical performance, water-tolerant and cost significantly reduce.
A kind of phenolate xylogen tackiness agent, composition of raw materials, with parts by weight, consists of:
Wherein the relation of the amount of main an acidic catalyst add-on and total an acidic catalyst is no less than the no more than 40wt% of 10wt%.
The preparation method of described a kind of phenolate xylogen tackiness agent is:
The preparation of a, phenolate xylogen:
At ambient pressure, take phenol as phenolate reagent, in 60 ~ 80 DEG C, add the 1st batch of xylogen, add main and auxiliary an acidic catalyst respectively afterwards, then add the 2nd batch of xylogen, first 2 batches add xylogen total amount 40 ~ 60%, insulation reaction 5 ~ 20min, afterwards in 80 ~ 95 DEG C, 1 batch of xylogen is added at interval of 5 or 10min, divide 2 ~ 3 batches and add remaining xylogen, be warming up to 100 ~ 130 DEG C, insulation reaction 5 ~ 60min, cooling, obtains phenolate xylogen.
Wherein the add-on of the 1st batch of xylogen is relevant with the add-on of phenol, and the add-on being specially the 1st batch of xylogen is no less than the no more than 60wt% of 40wt% of the total consumption of phenol.
The synthesis of b, phenolate xylogen tackiness agent:
In atmospheric conditions, to in the reactor that phenolate xylogen is housed, add basic catalyst and a certain amount of water, in 35 ~ 55 DEG C of insulation reaction 10 ~ 20min, divide and add aldehyde material four times, first add 45 ~ 55% of required aldehyde material total amount, slowly be warming up to 80 ~ 95 DEG C, add 20 ~ 25% of required aldehyde material total amount again, in 80 ~ 95 DEG C of insulation reaction 5 ~ 30min, add 10 ~ 15% of required aldehyde material total amount again, in 80 ~ 95 DEG C of insulation reaction 15 ~ 60min, remaining aldehyde material is added in the most backward reactor, in 80 ~ 95 DEG C of insulation reaction, the method of falling bubble of employing or painting-4 agar diffusion method measure the viscosity of product to desirable value, add the solid content that remaining water regulates product, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Described main and auxiliary an acidic catalyst, its main an acidic catalyst is trifluoroacetic acid, and auxiliary acid catalyzer is one or both in hydrochloric acid, sulfuric acid or phosphoric acid.
Described basic catalyst is sodium hydroxide or potassium hydroxide.
Described aldehyde material is one or both in formaldehyde (content of formaldehyde solution is 36 ~ 40%), paraformaldehyde (polymerization degree is 8 ~ 12), acetaldehyde or furfural.
Described xylogen is sodium lignosulfonate or sulfonation bamboo pulp alkali lignin.
Described sodium lignosulfonate is the sodium lignosulfonate of technical grade, and its lignin component content is not less than 60%, and weight-average molecular weight is not higher than 60000, and number-average molecular weight is not higher than 25000.
Described sulfonation bamboo pulp alkali lignin is the sulfonation bamboo pulp alkali lignin that the bamboo pulp alkali lignin of technical grade is prepared through catalyzed oxidation, sulfonation, drying process, and its lignin component content is not less than 75%, and weight-average molecular weight is not higher than 40000, and number-average molecular weight is not higher than 15000.
Described phenolate xylogen tackiness agent, relative to traditional synvaren, the alternative amount of xylogen Pyrogentisinic Acid is up to 50 ~ 80%, and cost can reduce about 40%.
Described phenolate xylogen tackiness agent solid content used water regulates, pH:8.0 ~ 11.0 are (by 30% solid content, 25 DEG C), free phenol content≤0.40% (by 40% solid content), free formaldehyde content≤0.12% (by 40% solid content).
Described phenolate xylogen tackiness agent has good mobility, can according to practical use, regulate the factors such as formula, technique, solid content, viscosity, prepare the phenolate xylogen tackiness agent of different purposes, as: the phenolate xylogen tackiness agent for paper impregnated adhesive process, the phenolate xylogen tackiness agent for bamboo plywood bamboo mat, bamboo curtain splint, thin bamboo strips used for weaving and bamboo chip gum dipping process, phenolate xylogen tackiness agent for wood plywood coating technique, etc.
Described phenolate xylogen tackiness agent has good stability in storage, shelf lives >30 days (25 DEG C).
The present invention creates and optimizes the phenolate xylogen of the high phenol amount of substituting and the recipe optimization of tackiness agent thereof, by the thermochemistry phenolate technology of great many of experiments improvement for many years, can obtain the phenolate xylogen of high reaction activity.In the basic conditions, this phenolate xylogen directly can replace phenol, reacts with aldehyde material, obtains phenolate xylogen tackiness agent.This phenolate xylogen tackiness agent has the features such as good fluidity, shelf-stable, easy construction, compared to traditional synvaren, also have concurrently safety and environmental protection, main raw material renewable, the feature such as significantly can to reduce costs.
Use the impregnated paper, bamboo/wood plywood etc. of phenolate xylogen production of adhesive of the present invention, there is the features such as excellent in mechanical performance, water-tolerant, safety and environmental protection.
The industrial lignin that the present invention adopts is mainly derived from sodium lignosulfonate and bamboo pulp alkali lignin prepared by paper-making pulping waste liquid, compared to general modified phenol formaldehyde resin adhesive with pulping waste liquor stick technology, the alternative amount of xylogen Pyrogentisinic Acid of the present invention is up to 50 ~ 80%, not only significantly reduce the cost of tackiness agent, and considerably reduce the demand of synvaren industry to petrochemicals phenol, simultaneously, also the pollution that the discharge decreasing papermaking wastewater to a certain extent causes environment, accelerate the industrial applications process of the renewable polymer wood quality of natural green.
Embodiment
Below in conjunction with the embodiment of the application, the technical scheme of the application is described in detail, but following embodiment is only understand the present invention, and the application can not be limited, embodiment in the application and the feature in embodiment can combine mutually, and the multitude of different ways that the application can be defined by the claims and cover is implemented.
Embodiment 1
To Teflon stir is housed, spherical condensation tube, 200.0g phenol is added in 2500mL five mouthfuls of flasks of tantalum alloy temperature sensor, be warming up to 60 ~ 65 DEG C, add 100.0g sulfonation bamboo pulp alkali lignin in order respectively, 6.0g trifluoroacetic acid, the sulfuric acid 24.0g of 9mol/L, 50.0g sulfonation bamboo pulp alkali lignin, insulation reaction 10min, be warming up to 80 ~ 85 DEG C, add 75.0g sulfonation bamboo pulp alkali lignin, insulation reaction 5min, add 75.0g sulfonation bamboo pulp alkali lignin again, be warming up to 105 ~ 115 DEG C, insulation reaction 30min, be quickly cooled to less than 45 DEG C, add alkali lye 193.3g (58.0g sodium hydroxide is dissolved in the water of 135.3g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 10min, add formaldehyde 300.0g, acetaldehyde 12.0g, after being slowly warming up to 90 DEG C, add formaldehyde 132.0g, acetaldehyde 5.4g, in 90 DEG C of insulation reaction 10min, add formaldehyde 75.0g again, acetaldehyde 3.0g, in 94 DEG C of insulation reaction 40min, add formaldehyde 93.0g again, acetaldehyde 3.6g, slowly be warming up to 90 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 450.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 26 ~ 28%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Comparative example 1
To Teflon stir is housed, spherical condensation tube, 200.0g phenol is added in 2500mL five mouthfuls of flasks of tantalum alloy temperature sensor, be warming up to 60 ~ 65 DEG C, add 100.0g sulfonation bamboo pulp alkali lignin in order respectively, the sulfuric acid 24.0g of 9mol/L, 50.0g sulfonation bamboo pulp alkali lignin, insulation reaction 10min, be warming up to 80 ~ 85 DEG C, add 75.0g sulfonation bamboo pulp alkali lignin, insulation reaction 5min, add 75.0g sulfonation bamboo pulp alkali lignin again, be warming up to 105 ~ 115 DEG C, insulation reaction 30min, be quickly cooled to less than 45 DEG C, add alkali lye 193.3g (58.0g sodium hydroxide is dissolved in the water of 135.3g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 10min, add formaldehyde 300.0g, acetaldehyde 12.0g, after being slowly warming up to 90 DEG C, add formaldehyde 132.0g, acetaldehyde 5.4g, in 90 DEG C of insulation reaction 10min, add formaldehyde 75.0g again, acetaldehyde 3.0g, in 94 DEG C of insulation reaction 40min, add formaldehyde 93.0g again, acetaldehyde 3.6g, slowly be warming up to 90 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 450.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 26 ~ 28%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 2
To Teflon stir is housed, spherical condensation tube, 125.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 75 ~ 80 DEG C, add 70.0g sodium lignosulfonate respectively in order, 9.0g trifluoroacetic acid, the sulfuric acid 27.0g of 12mol/L, 15.0g concentrated hydrochloric acid, 90.0g sodium lignosulfonate, insulation reaction 15min, be warming up to 85 ~ 90 DEG C, add 90.0g sodium lignosulfonate, insulation reaction 10min, add 70.0g sodium lignosulfonate again, insulation reaction 5min, add 55.0g sodium lignosulfonate again, be warming up to 115 ~ 120 DEG C, insulation reaction 45min, be quickly cooled to less than 45 DEG C, add alkali lye 283.0g (85.0g potassium hydroxide is dissolved in the water of 198.0g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 20min, add formaldehyde 280.0g, after being slowly warming up to 92 DEG C, add formaldehyde 123.5g, in 90 DEG C of insulation reaction 15min, add formaldehyde 70.0g again, in 90 DEG C of insulation reaction 30min, add formaldehyde 87.3g again, slowly be warming up to 94 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 350.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 28 ~ 30%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 3
To Teflon stir is housed, spherical condensation tube, 225.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 60 ~ 70 DEG C, add 100.0g sodium lignosulfonate respectively in order, 5.0g trifluoroacetic acid, 20.0g concentrated hydrochloric acid, 60.0g sodium lignosulfonate, insulation reaction 5min, be warming up to 85 ~ 90 DEG C, add 60.0g sodium lignosulfonate, insulation reaction 10min, add 55.0g sodium lignosulfonate again, be warming up to 110 ~ 115 DEG C, insulation reaction 25min, be quickly cooled to less than 45 DEG C, add alkali lye 213.0g (64.0g sodium hydroxide is dissolved in the water of 149.0g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 330.0g, after being slowly warming up to 85 DEG C, add formaldehyde 145.0g, in 90 DEG C of insulation reaction 30min, add formaldehyde 82.5g again, in 90 DEG C of insulation reaction 15min, add formaldehyde 104.5g again, slowly be warming up to 90 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 400.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 25 ~ 28%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Comparative example 2
To Teflon stir is housed, spherical condensation tube, 225.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 60 ~ 70 DEG C, add 100.0g sodium lignosulfonate respectively in order, 5.0g trifluoroacetic acid, 20.0g concentrated hydrochloric acid, 60.0g sodium lignosulfonate, insulation reaction 5min, be warming up to 85 ~ 90 DEG C, add 60.0g sodium lignosulfonate, insulation reaction 10min, add 55.0g sodium lignosulfonate again, be warming up to 110 ~ 115 DEG C, insulation reaction 25min, be quickly cooled to less than 45 DEG C, add alkali lye 213.0g (64.0g sodium hydroxide is dissolved in the water of 149.0g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 475.0g, after being slowly warming up to 85 DEG C, in 90 DEG C of insulation reaction 30min, add formaldehyde 187g again, in 90 DEG C of insulation reaction 15min, slowly be warming up to 90 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 400.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 25 ~ 28%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 4
To Teflon stir is housed, spherical condensation tube, 250.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 60 ~ 70 DEG C, add 100.0g sulfonation bamboo pulp alkali lignin in order respectively, 4.0g trifluoroacetic acid, 8.0g concentrated hydrochloric acid, 4.0g strong phosphoric acid, 50.0g sulfonation bamboo pulp alkali lignin, insulation reaction 5min, be warming up to 85 ~ 90 DEG C, add 50.0g sulfonation bamboo pulp alkali lignin, insulation reaction 5min, add 50.0g sulfonation bamboo pulp alkali lignin again, be warming up to 115 ~ 120 DEG C, insulation reaction 20min, be quickly cooled to less than 45 DEG C, add alkali lye 85.0g (25.0g sodium hydroxide is dissolved in the water of 60.0g), water 300.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 198.0g, paraformaldehyde 47.5g, after being slowly warming up to 80 DEG C, add formaldehyde 87.2g, paraformaldehyde 21.4g, in 90 DEG C of insulation reaction 10min, add formaldehyde 49.5g again, paraformaldehyde 11.9g, in 85 DEG C of insulation reaction 45min, add formaldehyde 61.4g again, paraformaldehyde 14.3g, slowly be warming up to 80 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 200.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, adopt coating technique to carry out the applying glue of wood plywood, at 130 ~ 140 DEG C, under the hot pressing condition of 8 ~ 12MPa, 2.0min/mm, carry out the preparation of wood plywood.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Comparative example 3
To Teflon stir is housed, spherical condensation tube, 250.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 60 ~ 70 DEG C, add 150.0g sulfonation bamboo pulp alkali lignin in order respectively, 4.0g trifluoroacetic acid, 8.0g concentrated hydrochloric acid, 4.0g strong phosphoric acid, insulation reaction 5min, be warming up to 85 ~ 90 DEG C, add 100.0g sulfonation bamboo pulp alkali lignin, insulation reaction 5min, be warming up to 115 ~ 120 DEG C, insulation reaction 20min, be quickly cooled to less than 45 DEG C, add alkali lye 85.0g (25.0g sodium hydroxide is dissolved in the water of 60.0g), water 300.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 198.0g, paraformaldehyde 47.5g, after being slowly warming up to 80 DEG C, add formaldehyde 87.2g, paraformaldehyde 21.4g, in 90 DEG C of insulation reaction 10min, add formaldehyde 49.5g again, paraformaldehyde 11.9g, in 85 DEG C of insulation reaction 45min, add formaldehyde 61.4g again, paraformaldehyde 14.3g, slowly be warming up to 80 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 200.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, adopt coating technique to carry out the applying glue of wood plywood, at 130 ~ 140 DEG C, under the hot pressing condition of 8 ~ 12MPa, 2.0min/mm, carry out the preparation of wood plywood.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 5
To Teflon stir is housed, spherical condensation tube, 150.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 70 ~ 80 DEG C, add 70.0g sodium lignosulfonate respectively in order, 8.0g trifluoroacetic acid, the sulfuric acid 35.0g of 12mol/L, 80.0g sodium lignosulfonate, insulation reaction 10min, be warming up to 85 ~ 95 DEG C, add 80.0g sodium lignosulfonate, insulation reaction 5min, add 70.0g sodium lignosulfonate again, insulation reaction 5min, add 50.0g sodium lignosulfonate again, be warming up to 125 ~ 128 DEG C, insulation reaction 55min, be quickly cooled to less than 45 DEG C, add alkali lye 270.0g (81.0g potassium hydroxide is dissolved in the water of 189.0g), water 125.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 279.0g, furfural 11.0g, after being slowly warming up to 85 DEG C, add formaldehyde 122.8g, furfural 5.0g, in 85 DEG C of insulation reaction 25min, add formaldehyde 69.7g again, furfural 2.8g, in 85 DEG C of insulation reaction 60min, add formaldehyde 86.5g again, furfural 3.3g, slowly be warming up to 85 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 400.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 27 ~ 30%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 6
To Teflon stir is housed, spherical condensation tube, 225.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 65 ~ 75 DEG C, add 100.0g sodium lignosulfonate respectively in order, 6.0g trifluoroacetic acid, 20.0g concentrated hydrochloric acid, 10.0g strong phosphoric acid, 60.0g sodium lignosulfonate, insulation reaction 5min, be warming up to 80 ~ 90 DEG C, add 60.0g sodium lignosulfonate, insulation reaction 5min, add 55.0g sodium lignosulfonate again, be warming up to 120 ~ 123 DEG C, insulation reaction 15min, be quickly cooled to less than 45 DEG C, add alkali lye 240.0g (72.0g sodium hydroxide is dissolved in the water of 168.0g), water 250.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 170.0g, paraformaldehyde 61.0g, after being slowly warming up to 92 DEG C, add formaldehyde 75.0g, paraformaldehyde 27.5g, in 88 DEG C of insulation reaction 20min, add formaldehyde 42.5g again, paraformaldehyde 15.2g, in 85 DEG C of insulation reaction 40min, add formaldehyde 52.8g again, paraformaldehyde 18.6g, slowly be warming up to 85 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 200.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, adopt coating technique to carry out the applying glue of wood plywood, at 130 ~ 140 DEG C, under the hot pressing condition of 8 ~ 12MPa, 2.0min/mm, carry out the preparation of wood plywood.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 7
To Teflon stir is housed, spherical condensation tube, 100.0g phenol is added in five mouthfuls of flasks of the 2500mL of tantalum alloy temperature sensor, be warming up to 75 ~ 80 DEG C, add 60.0g sodium lignosulfonate respectively in order, 10.0g trifluoroacetic acid, the sulfuric acid 38.0g of 13.5mol/L, 100.0g sodium lignosulfonate, insulation reaction 20min, be warming up to 85 ~ 95 DEG C, add 100.0g sodium lignosulfonate, insulation reaction 10min, add 80.0g sodium lignosulfonate again, insulation reaction 5min, add 60.0g sodium lignosulfonate again, be warming up to 125 ~ 130 DEG C, insulation reaction 35min, be quickly cooled to less than 45 DEG C, add alkali lye 297.0g (89.0g sodium hydroxide is dissolved in the water of 208.0g), water 150.0g, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 212.0g, paraformaldehyde 19.0g, after being slowly warming up to 85 DEG C, add formaldehyde 92.8g, paraformaldehyde 8.6g, in 85 DEG C of insulation reaction 20min, add formaldehyde 54.0g again, paraformaldehyde 4.8g, in 85 DEG C of insulation reaction 30min, add formaldehyde 65.7g again, paraformaldehyde 5.7g, slowly be warming up to 85 DEG C of insulation reaction, at interval of 3 ~ 5min, its viscosity is measured by the method for falling bubble, when falling after bubble viscosity reaches requirement to stop heating, and add 200.0g water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, adopt coating technique to carry out the applying glue of wood plywood, at 130 ~ 140 DEG C, under the hot pressing condition of 8 ~ 12MPa, 2.0min/mm, carry out the preparation of wood plywood.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 8 (anchor formula stirs, rotating speed 60rpm for enlarged experiment: 100L enamel still, steam heating)
10.00kg phenol is added in the enamel still of 100L, be warming up to 70 ~ 75 DEG C, add 4.00kg sulfonation bamboo pulp alkali lignin in order respectively, 0.25kg trifluoroacetic acid, 0.45kg concentrated hydrochloric acid, 0.25kg strong phosphoric acid, 2.00kg sulfonation bamboo pulp alkali lignin, insulation reaction 10min, be warming up to 80 ~ 90 DEG C, add 2.00kg sulfonation bamboo pulp alkali lignin, insulation reaction 10min, add 2.00kg sulfonation bamboo pulp alkali lignin again, be warming up to 113 ~ 115 DEG C, insulation reaction 15min, be quickly cooled to less than 45 DEG C, add alkali lye 10.00kg (3.00kg sodium hydroxide is dissolved in the water of 7.00kg), water 5.00kg, in 35 ~ 55 DEG C of insulation reaction 15min, add formaldehyde 13.80kg, after being slowly warming up to 92 DEG C, add formaldehyde 6.10kg, in 95 DEG C of insulation reaction 15min, add formaldehyde 3.50kg again, in 90 DEG C of insulation reaction 30min, add formaldehyde 4.30kg again, slowly be warming up to 92 DEG C of insulation reaction, at interval of 5 ~ 6min, its viscosity is measured with painting-4 agar diffusion methods, heating is stopped after viscosity reaches requirement, and add 15.00kg water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, tackiness agent being diluted with water to solid content is 27 ~ 28%, adopts gum dipping process to carry out the applying glue of bamboo plywood, at 140 ~ 150 DEG C, carries out the preparation of bamboo plywood under the hot pressing condition of 15 ~ 20MPa, 1.5min/mm.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
Embodiment 9 (enlarged experiment: 100L enamel still, steam heating, anchor stirrer, rotating speed 60rpm)
8.00kg phenol is added in the enamel still of 100L, be warming up to 75 ~ 80 DEG C, add 4.00kg sodium lignosulfonate respectively in order, 0.25kg trifluoroacetic acid, the sulfuric acid 0.45kg of 9mol/L, 0.40kg concentrated hydrochloric acid, 2.00kg sodium lignosulfonate, insulation reaction 15min, be warming up to 85 ~ 90 DEG C, add 3.00kg sodium lignosulfonate, insulation reaction 10min, add 3.00kg sodium lignosulfonate again, be warming up to 117 ~ 120 DEG C, insulation reaction 20min, be quickly cooled to less than 45 DEG C, add alkali lye 10.70kg (3.20kg potassium hydroxide is dissolved in the water of 7.50kg), water 5.00kg, in 35 ~ 55 DEG C of insulation reaction 10min, add formaldehyde 9.00kg, paraformaldehyde 1.50kg, after being slowly warming up to 90 DEG C, add formaldehyde 4.00kg, paraformaldehyde 0.65kg, in 90 DEG C of insulation reaction 20min, add formaldehyde 2.25kg again, paraformaldehyde 0.36kg, in 85 DEG C of insulation reaction 35min, add formaldehyde 2.80kg again, paraformaldehyde 0.45kg, slowly be warming up to 87 DEG C of insulation reaction, at interval of 5 ~ 6min, its viscosity is measured with painting-4 agar diffusion methods, heating is stopped after viscosity reaches requirement, and add 10.00kg water, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent.
Use above-mentioned phenolate xylogen tackiness agent, adopt coating technique to carry out the applying glue of wood plywood, at 130 ~ 140 DEG C, under the hot pressing condition of 8 ~ 12MPa, 2.0min/mm, carry out the preparation of wood plywood.
The performance of above-mentioned tackiness agent and glued board sees attached list 1.
The salient features table look-up of subordinate list 1 phenolate xylogen tackiness agent and prepared bamboo/wood plywood
Note: the viscosity of tackiness agent by value corresponding to survey solid content; Free formaldehyde and free phenol content, be all converted into value when tackiness agent solid content is 40%.
These are only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various change and conversion.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. prepare a method for phenolate xylogen tackiness agent, it is characterized in that comprising the steps:
The preparation of a, phenolate xylogen:
At ambient pressure, take phenol as phenolate reagent, in 60 ~ 80 DEG C, add the 1st batch of xylogen, add main and auxiliary an acidic catalyst respectively afterwards, then add the 2nd batch of xylogen, first 2 batches add xylogen total amount 40 ~ 60%, insulation reaction 5 ~ 20min, afterwards in 80 ~ 95 DEG C, 1 batch of xylogen is added at interval of 5 or 10min, divide 2 ~ 3 batches and add remaining xylogen, be warming up to 100 ~ 130 DEG C, insulation reaction 5 ~ 60min, cooling, obtains phenolate xylogen; The add-on of the 1st batch of xylogen is no less than the no more than 60wt% of 40wt% of the total consumption of phenol;
The synthesis of b, phenolate xylogen tackiness agent:
In atmospheric conditions, to in the reactor that phenolate xylogen is housed, add basic catalyst and a certain amount of water, in 35 ~ 55 DEG C of insulation reaction 10 ~ 20min, divide and add aldehyde material four times, first add 45 ~ 55% of required aldehyde material total amount, slowly be warming up to 80 ~ 95 DEG C, add 20 ~ 25% of required aldehyde material total amount again, in 80 ~ 95 DEG C of insulation reaction 5 ~ 30min, add 10 ~ 15% of required aldehyde material total amount again, in 80 ~ 95 DEG C of insulation reaction 15 ~ 60min, remaining aldehyde material is added in the most backward reactor, in 80 ~ 95 DEG C of insulation reaction, the method of falling bubble of employing or painting-4 agar diffusion method measure the viscosity of product to desirable value, add the solid content that remaining water regulates product, be cooled to rapidly less than 50 DEG C simultaneously, discharging, obtain phenolate xylogen tackiness agent, wherein
Above-mentioned raw materials formula, with parts by weight, consists of:
Phenol 100 parts
100 ~ 400 parts, xylogen
Main and auxiliary an acidic catalyst 6 ~ 51 parts
Basic catalyst 9 ~ 90 parts
100 ~ 900 parts, water
Aldehyde material 180 ~ 620 parts.
2. method according to claim 1, is characterized in that: described main an acidic catalyst is trifluoroacetic acid, and auxiliary acid catalyzer is one or both in hydrochloric acid, sulfuric acid or phosphoric acid.
3. method according to claim 1, is characterized in that: described basic catalyst is sodium hydroxide or potassium hydroxide.
4. method according to claim 1, is characterized in that: described aldehyde material is one or both in paraformaldehyde, acetaldehyde or the furfural that the content of solution is 36 ~ 40% formaldehyde, the polymerization degree is 8 ~ 12.
5. method according to claim 1, is characterized in that: described xylogen is sodium lignosulfonate or sulfonation bamboo pulp alkali lignin.
6. method according to claim 5, is characterized in that: described sodium lignosulfonate is the sodium lignosulfonate of technical grade, and its lignin component content is not less than 60%, and weight-average molecular weight is not higher than 60000, and number-average molecular weight is not higher than 25000.
7. method according to claim 5, it is characterized in that: described sulfonation bamboo pulp alkali lignin is the sulfonation bamboo pulp alkali lignin that the bamboo pulp alkali lignin of technical grade is prepared through catalyzed oxidation, sulfonation, drying process, its lignin component content is not less than 75%, weight-average molecular weight is not higher than 40000, and number-average molecular weight is not higher than 15000.
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